Process of oxidizing cymenes



Patented Nov. .17, .19 2

UNITED" STATE PnocEss F oxmrzmo CYMENES Robert C. Palmer and Carlisle 11. Bibb, Pensacola, Fla., assignors to Newport Industries, Inc., Pensacola, Fla., a corporation of Delaware No Drawing.

Application March 19, 1941,

Serial No. 384,994 3 Claims. (01. zoo-592i This invention relates to a process of oxidizing cymenes and to products produced thereby, particularly mixtures of tertiary alcohols and ketones, such as dimethyl tolyl carbinol and p-methyl acetophenone. Such mixtures are useful for their solvent and wetting properties, which are, in general, similar to those of pine oil.

In our copending application, Serial No. 303,-

.026, filed November 6, 1939, entitled Process of preparing cumic acid, of which the present is a continuation-impart, we have described and claimed the catalytic oxidation of a cymene to produce cumic acid. The present application is directed more particularly to the recovery of a mixture of tertiary alcohols and ketones, substantially free from cumic and other acids, the

a mixture of tertiary alcohols and ketones, particularly of dimethyl tolyl carbinol and p-methyl acetophenone, having useful solvent and wettin properties.

A mixture of manganese acetate containing 4 mols of water with lead acetate containing 3 mols of water is intimately ground and fused at about 130 C., until the product becomes anhydrous and solid. The mixture should be held at this temperature, preferably, until a slight brown discoloration appears. The solid mixture is then cooled in a dry atmosphere and ground to a fine powder. The catalytic activity of the mixture is not critical as regards the proportion of manganese to lead, but 2 parts of manganese acetate to 1 partof lead acetate have been found to be very satisfactory.

The following example will serve to illustrate a preferred embodiment of our process for preparing a mixture of dimethyl tolyl carbinol and methyl acetophenone from p-cymene:

200 gallons of p-cymene are placed in a suitable vessel equipped with heating, cooling and the introduction of air the'reinto.

agitating means, as well as with a pipe or conduit leading down into the body of the p-cymene for lbs., corresponding roughly with 2% by weight, of a catalyst, such as the mixture of 'lead and manganese acetate above described, are added and the temperature raised to about 45 C.,.where it is held for about 2 hours. Air is introduced into the charge of p-cymene at the rate of about Other and further important objects of this i invention will become apparent from the. following description and appended claims.

The catalysts that we have found to be most satisfactory for our purpose are the oxygen containing compounds of the so-called heavy metals, particularly of such metals as manganese, lead, cobalt, iron, nickel, copper, vanadium, chromium and mercury. The oxides, hydroxides, or organic salts of any of these metals, or combinations tures of lead and manganese compounds give the optimum catalytic action.

The following will serve as an example of one method of preparing a preferred catalyst com- 17 cu. ft. per minute, while at the. same time agitating the charge vigorously. After the 2 hour period, the temperature can be brought down to 30 C. and the process continued for an additional period of about 72 hours. The degree of oxidation taking place can be followed by determining the specific gravity of the product.

The specific gravity may, for instance, be allowed to increase from 0.861 for p-cymene itself, to 0.994 for a mixture of cymene, cumic acid, dimethyl tolyl carbinol, p-methyl acetophenone and minor proportions of aldehydes and oxides. At the latter specific gravity, the crude oxidized cymen'e reaction mass will usually contain around 20% of its weight as cumic acid, the balance beingfor distillation. In order to remove these peroxide-like bodies, after the completion of the oxidation stage, the air is turned off and the temperaprisingamixture of lead and manganese acetate: ture of the charge in the still is advanced to temperature by circulation of cold water, if necessary, through the jacket of the still. Decomposition of the thermally decomposable oxygen containing compounds takes place rapidly atthe temperature indicated, but by providing ample vacuum capacity and by circulating cooling water through the jacket of the still, the rate of evolution of non-condensible gases can be satisfactorily controlled so as to prevent substantial loss or vacuum and consequent rise in the boiling temperature of the charge in the still.

The resulting crude reaction mass, freed from peroxide-like bodies and having a volume of about 190 gallons, is next washed once with a slight excess of dilute hydrochloric acid, as for instance, an amount of 6% hydrochloric acid suflicient to react with the metal compounds present and to effect their removal from the crude reaction mass. This step is preferred, but not essential, for the purpose of putting the resulting crude reaction mass in a condition which will not cause emulsions to persist when it is subsequently washed with an aqueous alkali solution to separate the cumic acid.

The crude reaction mass isthen given a water wash of about 200 gallons to remove the remain- I ing chlorides.

It is finally washed once with a slight excess (based on the acid content) of a 6% solution of sodium hydroxide, or other equivalent alkali solution, to remove the cumic acid as the alkali metal salt. The aqueous alkali ex ing alkali wash, the mixture of tertiary alcohols and ketones, particularly dimethyl tolyl carbinol and \p-methyl acetophenone, and unreacted cymene, is subjected to fractional distillation under a relatively high vacuum. For instance,

the mixture may be charged into a jacketed still and the charge in the still heated by steam in .the jacket to about 100 C., whiledrawing -a vacuum of around 20 to 30 mm. of mercury, absolute pressure, on the still. These conditions of temperature and vacuum are maintained until practically all of the hydrocarbons have been distilled oil. The pressure is then dropped to around to mm. to take off a cut consisting largely of the dimethyl tolyl carbinol and methyl acetophenone. -The proper boiling range for the cut 2,so2;4oe binol and ketone are not separable by distil1ation, this control affords the most satisfactory means of varying the proportions of the main constituents of the mixture.

Within the range of compositions above given, the refractive index at C. will lie between 1.51 and 1.53, with 1.5200 as typical of the preferred "composition. The specific gravity at 15.5/4 C.

The time of oxidation can be considerably reduced if a small quantity, such as 10%, of the crude oxidation reaction mass of a previous run is added to a new batch to be oxidized. This assists in the activation of the catalyst, which,

will,,of course, depend upon the degree of vacum, and since the degree of vacuum mayvary considerably within the still, it is impossible to give any specific directions. At a vacuum of 1 mm. of mercury, absolute pressure, for instance, the boiling range may be between '77 and 89 C.

The composition of the cut so separated will, in general, run between and 90% of tertiary alcohols, principally dimethyl tolyl carbinol, and between 40 and 10% of ketones, mostly methyl acetophenone. A preferred composition is between 75 and.85% oi. dimethyl tolyl carbinol and between 25 and 15% of methyl acetophenone, with traces of aldehydes and oxides.

The proportion of carbinol to ketone can be varied by controlling the degree of oxidation effected. For example, if the oxidation is carried further to use up more of the cymene, the proportion of ketone to carbinol in the mixture increases. The control of the extent of oxidation thus provides a method of obtaining the desired proportion of carbinol to ketone. Since the careven at ordinary room temperatures, may become so active that with good agitation practically all of the oxygen of the air used is consumed in a single pass. Furthermore the addition of some of a previous crude reaction mass to a new batch causes the reaction to take place rapidly at the lowest temperature. It is possible, although this compounds which are more soluble or more easily dispersed than the acetates.

The temperature of oxidation may be varied either way from the 30 C. specified in the foregoing exampl. At temperatures much below 30 0., the rate of oxidation becomes impracticably low. At temperatures above 30 CI, the

rate of the reaction becomes greater, but teniperatures below 50 C. are preferred.

The cymene used as the starting material does not have to be pure p-cymene, but a similar process starting with a mixture of p-cymene and p-menthane, using optionally higher temperatures, is described and claimed in .our opending application entitled Process of Oxidizmg Cy mene and P-Menthane and Products Therefrom,

filed of even date herewith. The extent to which the oxidation is carried in any given batch may be varied over a considerable range, by controlling the rate of intro- From a practical standpoint, however, the proportion of catalyst will, in general, lie within the range of from 0.1 to 5% of the weight of the charge.

Other methods of contacting air, or molecular oxygen, with the cymene in the presence of an oxidizing catalyst are also effective in producing the desired mixture of tertiary alcohols and ketones. For example, the cymene may be sprayed into air and allowed to collect, the air replaced and the product resprayed until it is sufliciently oxidized. Alternatively, the cymene and catalyst may be caused to flow down through a partially filled or packed tower, up through which a stream of air is passed. So long as air, or molecular oxygen, is brought into intimate contact with the the oxidation cymene and catalyst, oxidation is effected. For the purposes of this specification and claims, air and oxygen are considered equivalents and are herein referred to generically as molecular oxygen.

It will, of course, be understood that various details of the process may be varied through a wide range without departing from the principles of this invention and it is, therefore, not the purpose to limit the patent granted hereon otherwise than necessitated by the scope of the appended claims.

We claim as our invention:

1. The process of oxidizing a cymene to recover a mixture of alcohols and ketones therefrom, which comprises subjecting a cymene in liquid phase to the action of molecular oxygen in the presence of an oxidation catalyst selected from the group consisting of oxides, hydroxides, and carboxylic acid salts of heavy metals at a temperature below 50 C. until a substantial proportion of the cymene has been converted into a mixture of acids, alcohols, and ketones, removing the acids, fractionally distilling the remaining mixture to separate unreacted cymene from the alcohols and ketones, and recovering the alcohols and ketones in admixture substantially free from said acids and unreacted cymene.

2. The process of oxidizing a cymene to recover a mixture of alcohols and ketones therefrom, 30

which comprises subjecting a cymene in liquid phase to the action of molecular oxygen in the presence of an oxidation catalyst comprising both lead and manganese compounds selected from the group consisting of oxides, hydroxides, and carboxylic acid salts of said metals at a temperature below about 50 C. until a substantial proportion of the cymene has been converted into a mixture of acids, alcohols, and ketones, removing said acids, fractionally distilling the remaining mixture under high vacuum, and recovering the alcohols and ketones in admixture substantially free from said acids.

3. The process of converting p-cymene into a mixture of dimethyl tolyl carbinol and p-methyl acetophenone, which comprises subjecting pcymene in liquid phase to the action of molecular mass, and distilling the remaining reaction mass.

to separate unreacted cymene and recover a mixture of dimethyl tolyl carbinol and p-methyl acetophenone relatively free from acids.

ROBERT C. PALMER.- CARLISLE H. BIBB. 

